Nanowire preparation, methods, compositions, and articles

ABSTRACT

Nanowire preparation methods, compositions, and articles are disclosed. Such nanowires may be thicker than other nanowires and may be useful in devices requiring high electrical current densities.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/275,496, filed Oct. 18, 2011, which claimed benefit of U.S.Provisional Application No. 61/416,425, filed Nov. 23, 2010, entitledMIXED METAL OR METAL ION CATALYSIS OF METAL ION REDUCTION, METHODS,COMPOSITIONS, AND ARTICLES, which is hereby incorporated by reference inits entirety.

BACKGROUND

The general preparation of silver nanowires (10-200 aspect ratio) isknown. See, for example, Angew. Chem. Int. Ed. 2009, 48, 60, Y. Xia, Y.Xiong, B. Lim, S. E. Skrabalak, which is hereby incorporated byreference in its entirety. Such preparations typically employ Fe²⁺ orCu²⁺ ions to “catalyze” the wire formation over other morphologies. Thecontrolled preparation of silver nanowires having desired lengths andwidths, however, is not known. For example, the Fe²⁺ produces a widevariety of lengths or thicknesses and the Cu²⁺ produces wires that aretoo thick for many applications.

The metal ions used to catalyze wire formation are generally primarilyreported to be provided as a metal halide salt, usually as a metalchloride, for example, FeCl₂ or CuCl₂. See, for example, J. Jiu, K.Murai, D. Kim, K. Kim, K. Suganuma, Mat. Chem. & Phys., 2009, 114, 333,which refers to NaCl, CoCl₂, CuCl₂, NiCl₂ and ZnCl₂; Japanese patentapplication publication JP2009155674, which describes SnCl₄; S.Nandikonda, “Microwave Assisted Synthesis of Silver Nanorods,” M. S.Thesis, Auburn University, Aug. 9, 2010, which refers to NaCl, KCl,MgCl₂, CaCl₂, MnCl₂, CuCl₂, and FeCl₃; S. Nandikonda and E. W. Davis,“Effects of Salt Selection on the Rapid Synthesis of Silver Nanowires,”Abstract INOR-299, 240th ACS National Meeting, Boston, Mass., Aug.22-27, 2010, which discloses NaCl, KCl, MgCl₂, CaCl₂, MnCl₂, CuCl₂,FeCl₃, Na₂S, and NaI; Chinese patent application publicationCN101934377, which discloses Mn²⁺; Y. C. Lu, K. S. Chou, Nanotech.,2010, 21, 215707, which discloses Pd²⁺; and Chinese patent applicationpublication CN102029400, which discloses NaCl, MnCl₂, and Na₂S.

SUMMARY

At least some embodiments provide a method comprising: providing acomposition comprising at least one first reducible metal ion, at leastone second metal or metal ion, and at least one third metal or metalion, where the at least one second metal or metal ion differs in atomicnumber from that of the at least one first reducible metal ion, and theat least one third metal or metal ion differs in atomic number from boththe at least one first reducible metal ion and the at least one secondmetal or metal ion.

In at least some embodiments, the composition further comprises at leastone compound comprising the at least one first reducible metal ion.

In some cases, the composition further comprises one or more of:

at least one solvent, or one or more surfactants, or one or more acids,or one or more polar polymers. Such solvents, when used, may, forexample, comprise at least one polyol. Such polar polymers, when used,may, for example, comprise polyvinylpyrrolidinone.

In at least some embodiments, the at least one first reducible metal ioncomprises at least one of: at least one coinage metal ion, at least oneion of an element from IUPAC Group 11, or at least one ion of silver.

In some such methods, the at least one second metal or metal ioncomprises the at least one second metal in its 0, +1, +2, +3, +4, +5, or+6 oxidation state. In some cases, the at least one third metal or metalion comprises the at least one third metal in its 0, +1, +2, +3, +4, +5,or +6 oxidation state.

In at least some embodiments, the at least one second metal or metal ionor the at least on third metal or metal ion may comprise at least onetransition metal or ion of a transition metal. In at least someembodiments, both the at least one second metal or metal ion and the atleast one third metal or metal ion each comprise at least one transitionmetal or ion of a transition metal.

In some such methods, the at least one second metal or metal ioncomprises at least one transition metal or ion of a transition metal andthe at least one third metal or metal ion comprises at least one elementfrom IUPAC Group 14 or ion of an element from IUPAC Group 14.

In at least some embodiments, the at least one second metal or metal ioncomprises at least one of: iron, an ion of iron, cobalt, an ion ofcobalt, manganese, an ion of manganese, tin, an ion of tin, germanium,or an ion of germanium.

Other embodiments provide the at least one first metal produced by suchmethods. In at least some embodiments, such an at least one first metalmay comprise one or more nanowires, nanocubes, nanorods, nanopyramids,or nanotubes.

Still other embodiments provide articles comprising the at least onefirst metal produced by such methods.

These embodiments and other variations and modifications may be betterunderstood from the brief description of figures, description, exemplaryembodiments, examples, figures, and claims that follow. Any embodimentsprovided are given only by way of illustrative example. Other desirableobjectives and advantages inherently achieved may occur or becomeapparent to those skilled in the art. The invention is defined by theappended claims.

BRIEF DESCRPTION OF FIGURES

FIG. 1 shows an optical micrograph of the product of comparative Example1.

FIG. 2 shows a scanning electron micrograph of the product ofcomparative Example 1.

FIG. 3 shows an optical micrograph of the product of Example 2.

FIG. 4 shows a scanning electron micrograph of the product of Example 2.

FIG. 5 shows an optical micrograph of the product of comparative Example3.

FIG. 6 shows an optical micrograph of the product of comparative Example4.

FIG. 7 shows an optical micrograph of the product of Example 5.

DESCRIPTION

All publications, patents, and patent documents referred to in thisdocument are incorporated by reference herein in their entirety, asthough individually incorporated by reference.

U.S. application Ser. No. 13/275,496, filed Oct. 18, 2011, entitledNANOWIRE PREPARATION METHODS, COMPOSITIONS, AND ARTICLES, is herebyincorporated by reference in its entirety.

U.S. Provisional Application No. 61/416,425, filed Nov. 23, 2010,entitled MIXED METAL OR METAL ION CATALYSIS OF METAL ION REDUCTION,METHODS, COMPOSITIONS, AND ARTICLES, is hereby incorporated by referencein its entirety.

Applicants have recognized that a mixture of metals or metal ions, suchas, for example, Fe²⁺ with Co²⁺, or Sn²⁺ with Mn²⁺, or Sn²⁺ withGe²⁺,can be used to control the aspect ratios of silver nanowires.Nanowires made in the presence of such a mixture of metals or metal ionsmay be thicker than other nanowires and may be useful in devicesrequiring high electrical current densities.

The methods are also believed to be applicable to reducible metalcations other than silver cations, including, for example, reduciblecations of other IUPAC Group 11 elements, reducible cations of othercoinage metals, and the like. The methods may, in some embodiments,employ a mixture of more than two metals or metal ions, such as, forexample, a mixture of three, four, or more metals or metal ions. Themetals or metal ions may be in the same or different oxidation statesfrom each other. For example, one or more metals or metal ions may be intheir 0, +1, +2, +3, +4, +5, +6, or higher oxidation states, while oneor more other metal ions may be in the same or different oxidationstates.

The methods may also be used to prepare products other than nanowires,such as, for example, nanocubes, nanorods, nanopyramids, nanotubes, andthe like. Such products may be incorporated into articles, such as, forexample, transparent electrodes, solar cells, light emitting diodes,other electronic devices, medical imaging devices, medical imagingmedia, and the like.

Reducible Metal Ions and Metal Products

Some embodiments provide methods comprising reducing at least onereducible metal ion to at least one metal. A reducible metal ion is acation that is capable of being reduced to a metal under some set ofreaction conditions. In such methods, the at least one first reduciblemetal ion may, for example, comprise at least one coinage metal ion. Acoinage metal ion is an ion of one of the coinage metals, which includecopper, silver, and gold. Or such a reducible metal ion may, forexample, comprise at least one ion of an IUPAC Group 11 element. Anexemplary reducible metal ion is a silver cation. Such reducible metalions may, in some cases, be provided as salts. For example, silvercations might, for example, be provided as silver nitrate.

In such embodiments, the at least one metal is that metal to which theat least one reducible metal ion is capable of being reduced. Forexample, silver would be the metal to which a silver cation would becapable of being reduced.

Mixtures of Metals or Metal Ions

In some embodiments, the reduction of the reducible metal ion occurs inthe presence of at least one second metal or metal ion and at least onethird metal or metal ion, where the at least one second metal or metalion differs in atomic number from the at least one first reducible metalion, and where the at least one third metal or metal ion differs inatomic number from both the at least one first reducible metal ion andthe at least one second metal or metal ion.

In general, the at least one second metal or metal ion and the at leastone third metal or metal ion may, by themselves or in combination withother metals or metal ions, be referred to as a mixture of metals ormetal ions. Such a mixture of metals or metal ions may comprise onlymetals, or only metal ions, or both metals and metal ions. Non-limitingexamples of such mixtures include Fe²⁺ with Co²⁺, or Sn²⁺ with Mn²⁺, orSn²⁺ with Ge²⁺. The mixture may comprise more than two metals or metalions, such as, for example, a mixture of three, four, or more metals ormetal ions. The metals or metal ions may be in the same or differentoxidation states from each other. For example, one or more metals ormetal ions may be in their 0, +1, +2, +3, +4, +5, +6, or higheroxidation states, while one or more other metals or metal ions may be inthe same or different oxidation states.

In some embodiments, the mixture of metals or metal ions may comprise nometal ions but only metals that are not ions, such as, for example,metal carbonyls. In still other cases, the mixture of metals or metalions may comprise only metal ions. In yet still other cases, the mixtureof metals or metal ions may comprise both metals and metal ions. Forexample, the one or more metals or metal ions may all be in their +1,+2, +3, +4, +5, +6 or higher oxidation states, or the one or more metalsor metal ions may all be metals in their 0 oxidation state, or the oneor more metal or metal ions may comprise one or more metal ions in their+1, +2, +3, +4, +5, +6 or higher oxidation states and one or more metalsin their 0 oxidation state.

Nanowires made in the presence of such a mixture of metals or metal ionsmay be thicker than other nanowires and may be useful in devicesrequiring high electrical current densities.

Preparation Methods

A common method of preparing nanostructures, such as, for example,nanowires, is the “polyol” process. Such a process is described in, forexample, Angew. Chem. Int. Ed. 2009, 48, 60, Y. Xia, Y. Xiong, B. Lim,S. E. Skrabalak, which is hereby incorporated by reference in itsentirety. Such processes typically reduce a metal cation, such as, forexample, a silver cation, to the desired metal nanostructure product,such as, for example, a silver nanowire. Such a reduction may be carriedout in a reaction mixture that may, for example, comprise one or morepolyols, such as, for example, ethylene glycol (EG), propylene glycol,butanediol, glycerol, sugars, carbohydrates, and the like; one or moreprotecting agents, such as, for example, polyvinylpyrrolidinone (alsoknown as polyvinylpyrrolidone or PVP), other polar polymers orcopolymers, surfactants, acids, and the like; and one or more metalions. These and other components may be used in such reaction mixtures,as is known in the art. The reduction may, for example, be carried outat one or more temperatures from about 120° C. to about 190° C., or fromabout 80° C. to about 190° C.

Nanostructures, Nanostructures, and Nanowires

In some embodiments, the metal product formed by such methods is ananostructure, such as, for example, a one-dimensional nanostructure.Nanostructures are structures having at least one “nanoscale” dimensionless than 300 nm, and at least one other dimension being much largerthan the nanoscale dimension, such as, for example, at least about 10 orat least about 100 or at least about 200 or at least about 1000 timeslarger. Examples of such nanostructures are nanorods, nanowires,nanotubes, nanopyramids, nanoprisms, nanoplates, and the like.“One-dimensional” nanostructures have one dimension that is much largerthan the other two dimensions, such as, for example, at least about 10or at least about 100 or at least about 200 or at least about 1000 timeslarger.

Such one-dimensional nanostructures may, in some cases, comprisenanowires. Nanowires are one-dimensional nanostructures in which the twoshort dimensions (the thickness dimensions) are less than 300 nm,preferably less than 100 nm, while the third dimension (the lengthdimension) is greater than 1 micron, preferably greater than 10 microns,and the aspect ratio (ratio of the length dimension to the larger of thetwo thickness dimensions) is greater than five. Nanowires are beingemployed as conductors in electronic devices or as elements in opticaldevices, among other possible uses. Silver nanowires are preferred insome such applications.

Such methods may be used to prepare nanostructures other than nanowires,such as, for example, nanocubes, nanorods, nanopyramids, nanotubes, andthe like. Nanowires and other nanostructure products may be incorporatedinto articles, such as, for example, electronic displays, touch screens,portable telephones, cellular telephones, computer displays, laptopcomputers, tablet computers, point-of-purchase kiosks, music players,televisions, electronic games, electronic book readers, transparentelectrodes, solar cells, light emitting diodes, other electronicdevices, medical imaging devices, medical imaging media, and the like.

Exemplary Embodiments

U.S. Provisional Application No 61/416,425, filed Nov. 23, 2010,entitled MIXED METAL OR METAL ION CATALYSIS OF METAL ION REDUCTION,METHODS, COMPOSITIONS, AND ARTICLES, which is hereby incorporated byreference in its entirety, disclosed the following 39 non-limitingexemplary embodiments:

A. A method comprising:

-   providing a composition comprising:    -   at least one compound comprising at least one first reducible        metal ion,    -   at least one second metal or metal ion, said at least one second        metal or metal ion differing in atomic number from said at least        one first reducible metal ion,    -   at least one third metal or metal ion, said at least one third        metal or metal ion differing in atomic number from said at least        one first reducible metal ion and from said at least one second        metal or metal ion,    -   and at least one solvent; and-   reducing the at least one first reducible metal ion to at least one    first metal.

B. The method of embodiment A, wherein the composition further comprisesat least one protecting agent.

C. The method of embodiment B, wherein the at least one protecting agentcomprises at least one of: one or more surfactants, one or more acids,or one or more polar polymers.

D. The method of embodiment B, wherein the at least one protecting agentcomprises polyvinylpyrrolidinone.

E. The method of embodiment B, further comprising inerting the at leastone protecting agent.

F. The method of embodiment A, wherein the composition further comprisesat least one fourth metal or metal ion, said at least one fourth metaldiffering in atomic number from said at least one first reducible metalion, from said at least one second metal or metal ion, and from at leastone third metal or metal ion.

G. The method of embodiment A, wherein the at least one first reduciblemetal ion comprises at least one coinage metal ion.

H. The method of embodiment A, wherein the at least one first reduciblemetal ion comprises at least one ion of an element from IUPAC Group 11.

J. The method of embodiment A, wherein the at least one first reduciblemetal ion comprises at least one ion of silver.

K. The method of embodiment A, wherein the at least one compoundcomprises silver nitrate.

L. The method of embodiment A, wherein the at least one second metal ormetal ion comprises the at least one second metal in its 0, +1, +2, +3,+4, +5, or +6 valence state.

M. The method of embodiment L, wherein the at least one third metal ormetal ion comprises the at least one third metal in its 0, +1, +2, +3,+4, +5, or +6 valence state.

N. The method of embodiment A, wherein the at least one compoundcomprises at least one salt of said at least one second metal or metalion or of said at least one third metal or metal ion.

P. The method of embodiment N, wherein the at least one salt comprisesat least one chloride.

Q. The method of embodiment A, wherein the at least one second metal ormetal ion comprises at least one transition metal or ion of a transitionmetal.

R. The method of embodiment Q, wherein the at least one third metal ormetal ion comprises at least one transition metal or ion of a transitionmetal.

S. The method if embodiment Q, wherein the at least one third metalcomprises at least one element or ion of an element from IUPAC Group 14.

T. The method of embodiment A, wherein the at least one second metal ormetal ion or the at least one third metal or metal ion comprises iron oran ion of iron.

U. The method of embodiment A, wherein the at least one second metal ormetal ion or the at least one third metal or metal ion comprises cobaltor an ion of cobalt.

V. The method of embodiment A, wherein the at least one second metal ormetal ion comprises iron or an ion of iron and the at least one thirdmetal or metal ion comprises cobalt or an ion of cobalt.

W. The method of embodiment A, wherein the at least one second metal ormetal ion or the at least one third metal or metal ion comprisesmanganese or an ion of manganese.

X. The method of embodiment A, wherein the at least one second metal ormetal ion or the at least one third metal or metal ion comprises tin oran ion of tin.

Y. The method of embodiment A, wherein the at least one second metal ormetal ion comprises manganese or an ion of manganese and the at leastone third metal or metal ion comprises tin or an ion of tin.

Z. The method of embodiment A, wherein the at least one solventcomprises at least one polyol.

AA. The method of embodiment A, wherein the at least one solventcomprises at least one of: ethylene glycol, propylene glycol, glycerol,one or more sugars, or one or more carbohydrates.

AB. The method of embodiment A, wherein the composition has a ratio ofthe total moles of the at least one second metal or metal ion and the atleast one third metal or metal ion to the moles of the at least onefirst reducible metal ion from about 0.0001 to about 0.1.

AC. The method of embodiment A, wherein the composition has a molarratio of the at least one second metal or metal ion to the at least onethird metal or metal ion from about 0.01 to about 100.

AD. The method of embodiment A, wherein the reduction is carried out atone or more temperatures from about 120° C. to about 190° C.

AE. The method of embodiment A, further comprising inerting one or moreof: the composition, the at least one compound comprising at least onefirst reducible metal ion, the at least one second metal or metal ion,the at least one third metal or metal ion, or the at least one solvent.

AF. The at least one first metal produced according to the method ofembodiment A.

AG. At least one article comprising the at least one first metalproduced according to the method of embodiment A.

AH. The at least one article of embodiment AG, wherein the at least onefirst metal comprises one or more nanowires, nanocubes, nanorods,nanopyramids, or nanotubes.

AJ. The at least one article of embodiment AG, wherein the at least onefirst metal comprises at least one object having an average diameter ofbetween about 10 nm and about 500 nm.

AK. The at least one article of embodiment AG, wherein the at least onefirst metal comprises at least one object having an aspect ratio fromabout 50 to about 10,000.

AL. At least one metal nanowire with an average diameter of betweenabout 10 nm and about 150 nm, and with an aspect ratio from about 50 toabout 10,000.

AM. The nanowire of embodiment AL, wherein the at least one metalcomprises at least one coinage metal.

AN. The nanowire of embodiment AL, wherein the at least one metalcomprises at least one element of IUPAC Group 11.

AP. The nanowire of embodiment AL, wherein the at least one metalcomprises silver.

AQ. At least one article comprising the at least one metal nanowire ofembodiment AL.

EXAMPLES Example 1 (Comparative)

To a 500 mL reaction flask containing 200 mL ethylene glycol (EG), 1.2mL of 7.0 mM FeCl₂ in EG was added and degassed with argon using a glasspipette. Stock solutions of 0.77 M polyvinylpyrrolidinone (PVP, 55,000molecular weight) in EG and 0.25 M AgNO₃ in EG were also degassed withargon. 60 mL syringes of the PVP and AgNO₃ solutions were then prepared.The reaction mixture was heated to 145° C. under N₂ and, after thereaction mixture was held 10 minutes at the set point temperature, theAgNO₃ and PVP solutions were added at a constant rate over 25 minutesvia a 20 gauge TEFLON® fluoropolymer syringe needle. The reactionmixture was held at 145° C. for 90 minutes, after which samples weretaken for optical microscopy. The reaction mixture was then quenched inan ice bath, after which samples were taken for scanning electronmicroscopy.

FIG. 1 shows an optical micrograph of the reaction product, while FIG. 2shows a scanning electron micrograph of the reaction product. Based onthe measurements of at least 100 wires, the product had an averagediameter of 123±34 nm.

Example 2

To a 500 mL reaction flask containing 280 mL EG, 1.1 mL of 7.7 mM FeCl₂in EG and 1.0 mL of 7.3 mM CoCl₂ in EG was added. The reaction mixturewas stirred and degassed with nitrogen using a glass pipette for 2 hrs.Stock solutions of 0.77 M PVP in EG and 0.25 M AgNO₃ in EG were alsodegassed with nitrogen for 60 min. 20 mL syringes of the PVP and AgNO₃solutions were then prepared. The reaction mixture was heated to 145° C.under N₂ and, after the reaction mixture was held 10 minutes at the setpoint temperature, the AgNO₃ and PVP solutions were added at a constantrate over 25 minutes via a 12 gauge TEFLON® fluoropolymer syringeneedle. The reaction mixture was held at 145° C. for 90 minutes, afterwhich samples were taken for optical microscopy. The reaction mixturewas then allowed to cool to ambient temperature. 15 mL of the cooledreaction mixture was diluted with 35 mL of isopropanol (IPA),centrifuged for 15 minutes at 1500 rpm, decanted, then re-dispersed in 5mL IPA. The resulting mixture was sampled for scanning electronmicroscopy.

FIG. 3 shows an optical micrograph of the reaction product, while FIG. 4shows a scanning electron micrograph of the reaction product. Based onthe measurements of at least 100 wires, the product had an averagediameter of 160 ±58 nm. These wires were thicker than those of Example1.

Example 3 (Comparative)

To a 500 mL reaction flask containing 280 mL EG, 2.0 g of 17 mM offreshly prepared 15 mM GeCl₂·dioxane in EG was added. The reactionmixture was stirred and degassed with nitrogen using a TEFLON®fluoropolymer tube for 2 hrs. Stock solutions of 0.84 M PVP in EG and0.25 M AgNO₃ in EG were also degassed with nitrogen for 60 min. 20 mLsyringes of the PVP and AgNO₃ solutions were then prepared. The reactionmixture was heated to 145° C. under 0.5 L/min N₂, then the AgNO₃ and PVPsolutions were added at a constant rate over 25 minutes via a 12 gaugeTEFLON® fluoropolymer syringe needle. The reaction mixture was held at145° C. for 90 minutes, after the reaction mixture was allowed to coolto ambient temperature. 15 mL of the cooled reaction mixture was dilutedwith 35 mL of IPA, centrifuged for 15 minutes at 1500 rpm, decanted,then re-dispersed in 5 mL IPA.

FIG. 5 shows an optical micrograph of the reaction product, which hadcopious non-nanowire nanoparticles.

Example 4 (Comparative)

To a 500 mL reaction flask containing 280 mL EG, 4.4 g of 6.9 mM SnCl₂in EG was added. The reaction mixture was stirred and degas sed withnitrogen using a TEFLON® fluoropolymer tube for 2 hrs. Stock solutionsof 0.84 M PVP in EG and 0.25 M AgNO₃ in EG were also degassed withnitrogen for 60 min. 20 mL syringes of the PVP and AgNO₃ solutions werethen prepared. The reaction mixture was heated to 145° C. under 0.5L/min N₂, then the AgNO₃ and PVP solutions were added at a constant rateover 25 minutes via a 12 gauge TEFLON® fluoropolymer syringe needle. Thereaction mixture was held at 145° C. for 90 minutes, after the reactionmixture was allowed to cool to ambient temperature. 15 mL of the cooledreaction mixture was diluted with 35 mL of IPA centrifuged for 15minutes at 1500 rpm, decanted, then re-dispersed in 5 mL IPA.

FIG. 6 shows an optical micrograph of the reaction product, which hadcopious non-nanowire nanoparticles.

Example 5

To a 500 mL reaction flask containing 280 mL EG, 2.1 g of 9.3 mM SnCl₂in EG and 1.4 g of freshly prepared 15 mM GeCl₂·dioxane in EG was added.The reaction mixture was stirred and degassed with nitrogen using aTEFLON® fluoropolymer tube for 2 hrs. Stock solutions of 0.84 M PVP inEG and 0.25 M AgNO₃ in EG were also degassed with nitrogen for 60 min.20 mL syringes of the PVP and AgNO₃ solutions were then prepared. Thereaction mixture was heated to 145° C. under 0.5 L/min N₂, then theAgNO₃ and PVP solutions were added at a constant rate over 25 minutesvia a 12 gauge TEFLON® fluoropolymer syringe needle. The reactionmixture was held at 145° C. for 90 minutes, after the reaction mixturewas allowed to cool to ambient temperature. 15 mL of the cooled reactionmixture was diluted with 35 mL of IPA centrifuged for 15 minutes at 1500rpm, decanted, then re-dispersed in 5 mL IPA.

FIG. 7 shows an optical micrograph of the reaction product, which hadfewer non-nanowire nanoparticles than either of the reaction products ofcomparative Examples 3 or 4. By comparing FIG. 7 to FIGS. 5 and 6, it isapparent that the Sn²⁺/Ge²⁺ mixed metal ion catalyst was more selectivetoward nanowire production than either of the equivalent molarity Sn²⁺or Ge²⁺ non-mixed metal ion catalysts.

The invention has been described in detail with reference to particularembodiments, but it will be understood that variations and modificationscan be effected within the spirit and scope of the invention. Thepresently disclosed embodiments are therefore considered in all respectsto be illustrative and not restrictive. The scope of the invention isindicated by the appended claims, and all changes that come within themeaning and range of equivalents thereof are intended to be embracedtherein.

1. A method of producing metal nanowires with reduced nanoparticlecoproduction comprising: providing a composition comprising: a firstmolar quantity of at least one first reducible metal ion, a second molarquantity of at least one second metal or metal ion, said at least onesecond metal or metal ion comprising germanium or an ion of germanium,and a third molar quantity of at least one third metal or metal ion,said at least one third metal or metal ion comprising tin or an ion oftin; and reducing the at least one first reducible metal ion to at leastone first metal nanowire, wherein the ratio of (1) the sum of the secondmolar quantity and the third molar quantity to (2) the first molarquantity is from about 0.0001 to about 0.1.
 2. The method according toclaim 1, wherein the composition further comprises at least one compoundcomprising the at least one first reducible metal ion.
 3. The methodaccording to claim 1, wherein the composition further comprises at leastone solvent comprising at least one polyol.
 4. The method according toclaim 1, wherein the composition further comprises at least one of: oneor more surfactants, one or more acids, or one or more polar polymers.5. The method according to claim 1, wherein the at least one firstreducible metal ion comprises at least one of: at least one coinagemetal ion, at least one ion of an element from IUPAC Group 11, or atleast one ion of silver.
 6. The method according to claim 1, wherein theat least one second metal or metal ion comprises the at least one secondmetal in its 0, +1, +2, +3, +4, +5, or +6 oxidation state.
 7. The methodaccording to claim 1, wherein the at least one third metal or metal ioncomprises the at least one third metal in its 0, +1, +2, +3, +4, +5, or+6 oxidation state.
 8. The method according to claim 1, wherein theratio of the second molar quantity to the third molar quantity is fromabout 0.01 to about
 100. 9. The method according to claim 1, wherein theat least one first metal nanowire comprises one or more silvernanowires.